Lubricant composition



Dec. 8, 1959 11.1. GRoE-rcH LUBRICANT coMPosITIoN Filed April 2e, 195e OBK,

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INVENTOR. Dona/d J. Groec Arron/vn United States Patent O LUBRICANT COMPOSITION Donald J. Groetch, Chicago, Ill., assignor to Standard Oil Company, Chicago, Ill., a corporation of Indiana Application April 26, 1956, Serial No. 580,803 7 Claims. (Cl. 252--32.7)

This invention relates to improved lubricating oil compositions and more particularly relates to improved motor oil compositions which do not increase excessively the octane requirement of the spark ignition internal combustion engine in which said motor oil is used.

Present day motor oils for the lubrication of spark ignition combustion engines are usually blends of petroleum or mineral oils of suitable viscosity and one or more addition agents to impart various desired properties thereto.

Among the usual addition agents employed are socalled detergent type additives and V.I. improves, the latter being used to modify the viscosity-temperature characteristics of the oil. Among the various types of V.l. improves used are the oil-soluble polymerization products of an ester of acrylic acid or its a-alkyl or u-aryl substitution products and monohydric alcohols containing more than 4 carbon atoms, preferably from about 4 to about 18 carbon atoms.

Typical products are the polymers of amyl, hexyl, cyclohexyl, octyl, decyl, lauryl, cetyl and octadecyl esters of acrylic acid, a-methacrylic acid, tac-phenyl acrylic acid and other tat-substituted homologues of acrylic acid. Polymers of the type herein-described and the method of preparing the same are described in U.S. 2,091,627, 2,100,- 993, and 2,407,954. Such polymers are marketed by Rohm and Haas Company as viscosity index improvers and pour point depressors under the trade name Acryloid.

Among the so-calleddetergent type additives, a preferred product is a neutralized reaction product of a phosphorus sulfide, e.g. phosphorus pentasulde and a normally nongaseous hydrocarbon such as are described in U.S. 2,316,082 issued to C. M. Loane, et al., April 6, 1943, and more fully described hereinafter.

While the use of the above described V.I. improves and detergent type additives impart desired viscositytemperature characteristics to the oil and the desired detergency, it has been observed that the use of the described V.I. improvers alone or when used in combination with detergent-type additives results in a substantial octane requirement increase (hereinafter referred to as ORI) in the spark-ignition engine in which such oils are used. By octane requirement of an engine is meant the octane number required to suppress the knock in an engine induced by detonation of the fuel or by surface igition of the fuel due to glowing deposits in the combustion chamber of the engine. The cause of this octane requirement increase induced with motor oils containing viscosity index improvers and detergent additives of the types above described, is not fully understood; however, since many motor oils contain such Vl. improvers and detergent additives, it is highly desirous to eliminate this detrimental eiect on the octane requirement.

It is an object of the present invention to provide for a spark ignition internal combustion engine, a hydrocarbon oil composition, containing the polymer of an 2,916,447 Patented Dec. S, 1959 "ice *c ester of acrylic acid or of its a-alkyl or fx-aryl substitution products and a neutralized reaction product of the phosphorus sulfide and a hydrocarbon, which will substantially lower the octane number requirement increase normally induced by said additives.

Another object of the invention is to provide a method of substantially reducing the octane requirement of an engine normally induced by a hydrocarbon oil composition containing a V.I. improver and a detergent additive of the type described. Other objects and advantages of the herein described invention will become apparent from the following description thereof.

In accordance with the present invention, the octane number requirement increase (ORI) induced by sparkignition engine motor oils containing from about 0.5% to about 15% of the above-described oil-soluble polymer of an ester of acrylic acid or of its alpha-alkyl or alphaphenyl substitution products and a monohydric alcohol containing from 4 to about 18 carbon atoms, and from about 0.5% to about 10% of a neutralized polyvalent metal-containing phosphorusand sulfur-containing detergent additive, is substantially decreased by incorporating in such lubricating oil compositions from about 0.5% to about 10% of a condensation product of a long chain chlorinated alkyl hydrocarbon of from about 10 to about 50 carbon atoms and a monoor dinuclear aromatic compound;

A long chain alkyl-aromatic hydrocarbon condensation product suitable for use in the present invention is preferably the condensation product of a paraffin wax and naphthalene. The condensation product is prepared by heating a mixture of a chlorinated paraffin wax with the naphthalene to a temperature of from about F. to about 350 F., preferably in the approximate temperature range of 250 F. to 350 F. in the presence of a Friedel-Crafts type catalyst, such as aluminum chloride. Upon completion of the condensation, the sludge formed is removed and the sludge-free product neutralized with hot caustic and water-Washed. The wax-aromatic condensation products and their preparation are fully described in U.S. 1,963,917 and 1,963,918, issued to F. H. MacLaren lune 19, 1934, and U.S. 2,057,104, issued to F. H. MacLaren et al., October 13, 1936. The condensation products described in these patents are known as Pourex. Other similar condensation products, marketed as Paraow, are described in U.S. 1,815,022, issued to G. Davis, July 14, 1931, and U.S. 2,174,246, issued to Lieber, et al., September 26, 1939.

Other related condensation products which can be suitably used are condensation products of paraliin wax and a monoor di-nuclear alkylated hydroxy aromatic compound and their esters such as are described in U.S. 2,191,498-499 and U.S. 2,138,809, the condensation products of resinified monoor di-nuclear hydroxy aromatic compounds and chlorinated wax which are described in U.S. 2,061,008 and U.S. 2,062,676, and the acylated condensation products of a monoor di-nuclear hydroxy aromatic compound and chlorinated wax of the type described in U.S. 2,138,809.

While the above condensation products are all suitable for use in the present invention, they are all not equivalent in their effectiveness; the condensation products of chlorinated paraffin wax and naphthalene of the type described in the above MacLaren patents being preferred.

Of the detergent-type motor oil additives, a preferred product is the neutralized reaction product of a phosphorus sulfide and a normally non-gaseous hydrocarbon such as described in the above mentioned Patent U.S. 2,316,082 to Loane, et al. As taught in this patent, the preferred hydrocarbon constituent of the reaction is a mono-oleriic hydrocarbon polymer resulting from the polymerization of low molecular weight mono-oletin hydrocarbons, such as propylene, butenes, amylenes or copolymers thereof. Such polymers may be obtained by the polymerization of mono-olefins of less than 6 carbon atoms in the presence of a catalyst, such as sulfuric acid, phosphoric acid, boron uoride, aluminum chloride, or other similar halide catalysts of the Friedel-Crafts type.

The polymers employed are preferably mono-olefin polymers or mixtures of mono-olefin polymers and isomono-oleiin polymers having molecular weights ranging from about 150 to about 50,000 or more, and preferably from about 500 to about 10,000. Such polymers can be obtained, for example, by the polymerization in the liquid phase of a hydrocarbon mixture containing monoand isomono-olens, such as butylene and iso-butylene at a temperature of from about -80 F. to about 100 F. in the presence of a metal halide catalyst of the Friedel-Crafts type, such as for example, boron fluoride, aluminum chloride, and the like. In the preparation of these polymers, a hydrocarbon mixture containing isobutylene, butylenes and butanes recovered from petroleum gases, especially those gates produced in the crackinf7 of petroleum oils in the manufacture of gasoline, can be used.

Essentially paraflinic hydrocarbons, such as bright stock residuums, lubricating oil distillates, petrolatums, or paraiiin waxes, may be used.

Examples of other high molecular weight oletinic hydrocarbons which can be employed are cetene (C16), cerotene (C26), melene (C30), and mixed high molecular weight alkenes obtained by cracking petroleum oils.

Other preferred olefins suitable for the preparation of the phosphorus sulfide reaction products are oleins having at least 20 carbon atoms in the molecule of which from about 13 carbon atoms to about 18 carbon atoms, and preferably at least 15 carbon atoms, are in a long chain. Such olefins can be obtained by the dehydrogenation of alkyl halides, preferably long chain alkyl halides, particularly halogenated parain waxes.

Other hydrocarbons that can be reacted with a phosphorus sulfide are aromatic hydrocarbons, such as for example, benzene, naphthalene, toluene, xylene, diphenyl, and the like, or an alkylated aromatic hydrocarbon, such as for example, benzene having an alkyl substituent having at least four carbon atoms, and preferably at least eight carbon atoms, such as a long chain paraliin wax.

The phosphorus sulfide hydrocarbon reaction product can be readily obtained by reacting a phosphorus sulfide, for example P255, with the hydrocarbon at a temperature of from about 200 F. to about 500 F. and preferably from about 200 F. to about 400 F., using from about 1% to about 50%, and preferably from about 5% to about 25% of the phosphorus suliide in the reaction. It is advantageous to maintain a non-oxidizing atmosphere, such as for example, an atmosphere of nitrogen above the reaction mixture. Usually, it is preferably to use an amount of the phosphorus sulfide that will completely react with the hydrocarbon so that no further purification becomes necessary; however, an excess amount of phosphorus sulfide can be used and separated from the product by filtration or by dilution with a hydrocarbon solvent, such as hexane, filtering and subsequently removing the solvent by suitable means, such as by distillation. If desired, the reaction product can be further treated with steam at an elevated temperature of from about 100 F. to about 600 F.

The phosphorus sulfide-hydrocarbon reaction product normally shows a titratable acidity which is neutralized by treatment with a basic reagent. The phosphorus sulfide-hydrocarbon reaction product, when neutralized with a basic reagent, containing a metal constituent, is characterized by the presence or retention of the metal constituent of the basic reagent.

D The neutralized phosphorus sulfide-hydrocarbon reaction product can be obtained by treating the acidic reac- Cil tion product with a suitable basic compound, such as hydroxide, carbonate, oxide or sulfide of an alkaline earth metal, such as for example, calcium oxide, lime, barium hydroxide, barium oxide, etc. Neutralized reaction products containing a heavy metal constituent, such as for example, tin, titanium, aluminum, chromium, cobalt, zinc, iron, and the like, can be obtained by reacting a salt of the desired heavy metal with the phosphorus sulfide-hydrocarbon reaction product which has been treated with a basic reagent, such as above described.

T he above described neutralized reaction products of a phosphorus sulfide and a hydrocarbon can be used in combination with small amounts, eg. 0.01% to 5% of elemental sulfur or a sulfur-containing organic compound such as a sulfurized mineral oil, vegetable oil, animal oil, etc. as described in U.S. Re. 22,464, issued to C. D. Kelso April 4, 1944, or with sulfurized terpenes, such as sulfurized dipentene as described in U.S. 2,422,585, issued to T. H. Rogers et al. June 17, 1947.

Other neutralized phosphorus sulfide reaction products which are used are the reaction products of a phosphorus suliide and a fatty acid ester of the type described in U.S. 2,399,243; the phosphorus suliide-degras reaction products of U.S. 2,413,332; the reaction product of an alkylated phenol with the condensation product of P2S5 and turpentine of US. 2,409,877 and U.S. 2,409,878; the reaction product of a phosphorus suliide and stearonitrile of U.S. 2,416,807, etc.

The lubricating oil component of the herein described composition can be any suitable hydrocarbon or petroleum lubricating oil ranging from SAE 5W to SAE 50 oils having Saybolt Universal viscosities of from about seconds at 100 F. to 110 seconds at 210 F. The oils can be multiple graded oils such as SAE 5W-20, 10W-30,'20W`40 oils.

The eifectiveness of the above disclosed condensation products in reducing the octane requirement due to the presence of viscosity index improvers and detergent-type additives of the kind hereinabove described in the motor oil is illustrated by the data in Table I.

These data were obtained in tests conducted under the following conditions. The engine, a 1953 Oldsmobile engine, is operated with an oil temperature of 175 F. and a water temperature of F. on a one hour cycle consisting of twenty part throttle cycles and one 30-second full throttle acceleration, controlled by an automatic tuning mechanism. The conditions for the cycle test are the following:

Part Throttle Full Cycle (20) Throttle Cycle (l) 1,500 10 (road load) 100 The one hour test cycle is repeated until equilibrium octane requirement is reached. Deposits are then scraped from the combustion chambers and the octane requirement of the clean engine determined. The difference between the equilibrium octane requirement andthe octane requirement after deposit removal is the octanerequirement increase (ORI).

The eifectiveness of the herein described invention in reducing the ORI of a spark-ignition engine is clearly demonstrated by comparing the ORI values of Test No. l with Test No. 2, Test No. 3 with Test No. 4, and Test No. 6 with Tests Nos. 7 and 8 in Table I. In each of these sets of tests, the ORI obtained using a motor oil containing the Acryloid and the detergent additive (Test Nos. 1, 3 and 6) was substantially reduced when the defined condensation product was added to themotor oil containing the said other additives (Tests Nos. 2, 4, 7

Table I Percent Percent Percent Test No. Oil SAE Methacry- Deter- Condensa- Percent ORI ORI Grade late gent tion Paratone Benefit Polymer- Add.b Product W-20 5. 5 5. 0 5. 1 0. 0 5W-20 5. 5 5. 0 1. 0 2. 2 +2. 9 5W-20 4. 5 5. 0 5. 0 0. 0 5W-20 4. 5 5. 0 1. 0 1. 6 +3. 4 20W-40 5. 2 y 20W-40 5. 5 5. 0 6. 8 0. 0 20W-40 5. 5 5.0 4. 4 +2. 4 20W-40 5. 5 5. 0 4. 3 +2. 5 5W-20 5. 0 10. 5 4. 0 W-30 5. 0 1. 5 10. 5 4. 3

and SUS/210 F. of 3,700

V.I. improver and pour point depressor Acryloid 794" having a viscosity SUS/100 F. of 24,000

bDetergent additive consisting of 65.4% of a barlum-contaning neutralizedlreaction vproduct of P135 and a polybutcne of about 1,000 molecular weight, 14.8% sulfurlzed dipentene and 19.8% diluent oil. A solvent extracted 5W grade mineral lubricating oCondensation product of a chlorinated paratiin Wax ance With U.S. 1,963,918 supra.

oil.

and naphthalene made in accorddCondensation product of a chlorinated wax and phenol marketed as Santopour, made by acylating the chlorinated Wax-phenol condensation described in U.S. 2,138,809 supra. A polybutene V.I. improver Company.

and 8). Test No. `8 demonstrates the use of a condensation product of a paratlin wax and a hydroxyaromatic compound (phenol) in reducing the ORI produced by the presence of an Acryloid-type V.I. improver and a detergent additive in the motor oil. That the herein described condensation products are specific to reducing the ORI induced by Acryloid-type V.I. improvers and the herein dened detergent-type additives is shown by the ORI tests Nos. 9 and l0. In these tests a polybutene V.I. additive was used in combination with the defined detergent additive. As shown by the ORI of these tests, the condensation product had no beneiicial effect on the ORI.

The beneficial results obtained by the present invention as demonstrated by the above tabulated data is graphically shown by the accompanying drawing. Since engine octane requirement is affected by the oil volatility as well as by the presence of additives, the data with respect to oil volatility as shown by the 90% vapor temperature of the various base oils when subjected to an ASTM distillation under 1 mm. mercury, and the engine octane requirement increase of the various base oils used with additives of the type described herein have been plotted. Line A is a plot of the engine octane requirement increase (ORI) resulting from the use of motor oils containing an Acryloidtype V.I. improver and a barium-containing neutralized reaction product of P285 and a polybutene of about 1,000 molecular weight, and line B is a plot of the ORI obtained when the condensation product of a chlorinated paraffin wax and naphthalene is added to the motor oil compositions used in obtaining the data of line A.

Percentages given herein and in the appended claims are weight percentages unless otherwise indicated.

I claim:

l. A spark-ignition internal combustion engine lubricating oil composition comprising a major proportion of a petroleum lubricating oil and in combination therewith from about 0.5% to about of an oil-soluble polymeric alpha-methacrylic acid ester of a monohydric saturated aliphatic alcohol containing from about 4 to about 18 carbon atoms, from about 0.5% to about 10% of a polyvalent metal, phosphorus, and sulfur-containing neutralized reaction product of a phosphorus suliide and a normally non-gaseous hydrocarbon, lubricating oil detergent additive, and from about 0.5% to about 10% of a condensation product of a chlorinated long-chain alkyl hydrocarbon having from about 10 to about 50 carbon atoms and an aromatic compound selected from the class consisting of a mononuclear aromatic hydrocarbon, a mono-nuclear hydroxyaromatic compound, a diproduct with phthalyl chloride as having a viscosity SUS/210 F. of 3,000 marketed by Enjay nuclear aromatic hydrocarbon and a dinuclear hydroxyaromatic compound, said condensation product being used in an amount suiiicient to reduce the octane requirement increase induced by said ester and said detergent additive.

2. A spark-ignition internal combustion engine crankcase lubricating oil composition comprising a major proportion of a petroleum lubricating oil and in combination therewith from about 0.5% to about 15% of an oil-soluble polymeric alpha-methacrylic acid ester of a monohydric saturated alcohol containing from about 4 to about 18 carbon atoms, from about 0.5% to about 10% of a polyvalent metal-containing neutralized reaction product of a phosphorus sulde and a normally nongaseous hydrocarbon, and from about 0.5% to about 10% of a condensation product of a chlorinated paraiiin wax and naphthalene, said condensation product being used in an amount suiicient to reduce the increase in the octane requirement of the engine induced by said ester and said neutralized reaction product of a phosphorus sulfide and a hydrocarbon.

3. A lubricating oil composition as described in claim 2 in which the polyvalent metal-containing neutralized reaction product of a phosphorus sulfide and a normally non-gaseous hydrocarbon is an alkaline earth metalcontaining neutralized reaction product of P285 and an olenic hydrocarbon polymer having a molecular weight of at least about 150.

4. A lubricating oil composition as described in claim 3 in which the alkaline earth metal is barium.

5. A spark-ignition internal combustion engine crankcase lubricating oil composition comprising a major proportion of a petroleum lubricating oil and in combination therewith from about 0.5% to about 15% of a polymeric alkyl alpha-methacrylate having viscosity index improving and pour point depressing properties, from about 0.5% to about 10% of a barium-containing neutralized reaction product of P285 and a butylene polymer having a molecular Weight of from about to about 50,000, and from about 0.5% to about 10% of a condensation product or" a chlorinated paraffinA wax and naphthalene, said condensation product being used in an amount suicient to reduce the increase in the octane requirement of the engine induced by said methacrylate and said barium containing neutralized reaction product.

6. In the operation of a spark-ignition internal combustion engine being operated with a lead alkyl-containing motor fuel and lubricated with a hydrocarbon lubricating oil composition containing as a Vl. improving agent and pour point depressor an oil-soluble polymeric alpha-methacrylic acid ester of a monohydric saturated aliphatic alcohol containing from about 4 to about 18 carbon atoms and as a detergent additive a neutralized phosphorus sulfide-normally non-gaseous hydrocarbon reaction product containing a polyvalent metal, phosphorus and sulfur, which said methacrylic acid ester and said detergent additives increase the octane requirement of said engine, the method of reducing said octane requirement increase comprising lubricating said engine with said crankcase hydrocarbon lubricating oil composition containing in combination therewith a condensation product of a chlorinated long chain alkyl hydrocarbon having from about 10 to about 50 carbon atoms and an aromatic compound selected from the class consisting of a mononuclear aromatic hydrocarbon and a dinuclear aromatic hydrocarbon, a mononuclear hydroxyaromatic compound and a dinuclear hydroxyaromatic compound, said condensation product being added in a small but suicient amount to reduce the octane requirement increase induced by said methacrylic acid and said detergent additive.

7. The method of claim 6 in which the detergent additive is a barium-containing neutralized reaction product of P285 and a butylene polymer of about 1000 molecular weight and said condensation product is a condensation product of a chlorinated paraffin wax and naphthalene.

References Cited in the tile of this patent UNITED STATES PATENTS 2,073,080 VanPeski Mar. 9, 1937 2,316,080 Loane Apr. 6, 1943 2,344,988 Kavanagh Mar. 28, 1944 2,409,333 Wright Oct. 15, 1946 2,739,122 Kennerly Mar. 20, 1956 UNITED NSUSATES .CERTIFICATE OF CORRECTION Patent No. 2,916,447 1 V b December e, 1959 Denem 4Je Greene;y I

.I'b is hereby `certified that error appears in the printed specification of 'the above numbered patent requiring correction and that the Said .Letters Patent should lreadI as corrected below.

Column l linesZ, 29, arldO, for "improves" read kw-improxfers "--q column 3, line 22, for' "gates" read gases L73Y seme column 3, 1111 56, for preferably" read preferable and 6, Table I, 1n the signed end eee1ed this 17th dey of Mey 1960.,I

(SEAL) Attest:

KARL H. AXLINE f ROBERT c. WATSON Attesting Officer l v, Commissioner of Patents 

1. A SPARK-IGNITION INTERNAL COMBUSTION ENGINE LUBRICATING OIL COMPOSITION COMPRISING A MAJOR PROPORTION OF A PETROLEUM LUBRICATING OIL AND IN COMBINATION THEREWITH FROM ABOUT 0.5% TO ABOUT 15% OF AN OIL-SOLUBLE POLYMERIC ALPHA-METHACRYLIC ACID ESTER OF A MONOHYDRIC SATURATED ALIPHATIC ALCOHOL CONTAINING FROM ABOUT 4 TO ABOUT 18 CARBON ATOMS, FROM ABOUT 0.5% TO ABOUT 10% OF A POLYVALENT METAL, PHOSPHORUS, AND SULFUR-CONTAINING NEUTRALIZED REACTION PRODUCT OF A PHOSPHORUS SULFIDE AND A NORMALLY NON-GASEOUS HYDROCARBON, LUBRICATING OIL DETERGENT ADDITIVE, AND FROM ABOUT 0.5% TO ABOUT 10% OF A CONDENSATION PRODUCT OF A CHLORINATED LONG-CHAIN ALKYL HYDROCARBON HAVING FROM BOUT 10 TO ABOUT 50 CARBON ATOMS AND AN AROMATIC COMPOUND SELECTED FROM THE CLASS CONSISTING OF A MONONUCLEAR AROMATIC HYDROCARBON, A MONO-NUCLEAR HYDROXYAROMATIC COMPOUND, A DINUCLEAR AROMATIC HYDROCARBON AND A DINUCLEAR HYDROXYAROMATIC COMPOUND, SAID CONDENSATION PRODUCT BEING USED IN AN AMOUNT SUFFICIENT TO REDUCE THE OCTANE REQUIREMENT INCREASE INDUCED BY SAID ESTER AND SAID DETERGEN ADDITIVE. 